Novel polymers

ABSTRACT

The present invention relates to polymers comprising repeating unit(s) of the formula (I), and their use in electronic devices. The polymers according to the invention have excellent solubility in organic solvents and excellent film-forming properties. In addition, high charge carrier mobilities and high temperature stability of the emission color are observed, if the polymers according to the invention are used in polymer light emitting diodes (PLEDs).

The present invention relates to novel polymers comprising repeatingunit(s) of the formula I and their use in electronic devices. Thepolymers according to the invention have excellent solubility in organicsolvents and excellent film-forming properties. In addition, high chargecarrier mobilities and high temperature stability of the emission colorcan be observed, if the polymers according to the invention are used inpolymer light emitting diodes (PLEDs).

WO2006043539 discloses among others light-emitting polymer compoundswhich emit blue light and contain pyrene.

EP0964045 describes polymeric fluorescent substances showing visiblefluorescence in solid state, wherein the polymeric fluorescent substancecomprises one or more repeating units represented by the followingformula (1) and the amount of these repeating units is from 0.5% by moleto 100% by mole based on the total amount of repeating units:—Ar₁—CR₁═CR₂— (1) wherein Ar₁ represents a condensed polycyclic aromaticgroup which may be substituted with a substituent selected from a cyanogroup, an alkyl group, alkoxy group or alkylthio group having 1 to 20carbon atoms, an alkylsilyl group having 3 to 60 carbon atoms, analkylamino group having 1 to 40 carbon atoms, an aryl group or aryloxygroup having 6 to 20 carbon atoms, an arylalkenyl group or arylalkynylgroup having 8 to 20 carbon atoms, an aralkyl group having 7 to 14carbon atoms and a heterocyclic compound group having 4 to 14 carbonatoms, R₁ and R₂ each independently represents a group selected from ahydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl grouphaving 6 to 20 carbon atoms, a heterocyclic compound having 4 to 20carbon atoms and a cyano group.

Examples of Ar₁ are among other groups of formula

wherein, R₅ to R₂₀ each independently represents a group selected from ahydrogen atom, a cyano group, an alkyl group, alkoxy group or alkylthiogroup having 1 to 20 carbon atoms; an alkylsilyl group having 3 to 60carbon atoms; an alkylamino group having 1 to 40 carbon atoms; an arylgroup or aryloxy group having 6 to 20 carbon atoms; an arylalkenyl groupor arylalkynyl group having 8 to 20 carbon atoms; an aralkyl grouphaving 7 to 14 carbon atoms; and a heterocyclic compound group having 4to 14 carbon atoms.

There are a number of challenges faced with the introduction of organicEL displays when their performance is compared with existingtechnologies. Obtaining the exact color coordinates required by specificguidelines (i.e. NTSC) has been problematic. The operational lifetime ofthe EL device is still lower when contrasted to the existing inorganictechnology for cathode ray tubes (CRTs) and liquid crystal displays(LCDs). In addition, producing a material with a pure blue color and along lifetime is one of the greatest problems for this industry.

Accordingly, it is the object of the present invention to provide novelmaterials, which show significant advantages in color purity, deviceefficiency and/or operational lifetime, when incorporated inelectro-optical devices.

Said object is solved by the polymers of the present inventioncomprising repeating units of formula I. Organic light emitting devices(OLEDs), comprising the polymers of the present invention, can showsignificant advantages in color purity, device efficiency and/oroperational lifetime. In addition, the polymers can have good solubilitycharacteristics and relatively high glass transition temperatures, whichfacilitates their fabrication into coatings and thin films, that arethermally and mechanically stable and relatively free of defects. If thepolymers contain end groups which are capable of being crosslinked, thecrosslinking of such groups after the films or coating is formedincreases the solvent resistance thereof, which is beneficial inapplications wherein one or more solvent-based layers of material aredeposited thereon.

Hence, the present invention relates to polymers comprising repeatingunit(s) of the formula

R¹, R², R³, R⁴, R⁵ and R⁶ are independently of each other hydrogen, F,SiR¹⁰⁰R¹⁰¹R¹⁰², or an organic substituent, orR¹ and R², R³ and R⁴, and/or any of the substituents R¹, R², R³, R⁴, R⁵and/or R⁶, which are adjacent to each other, together form an aromatic,or heteroaromatic ring, or ring system, which can optionally besubstituted, m is 0, or an integer of 1, or 2,n1 and n2 are 0, or an integer 1, or 2,R¹⁰⁰, R¹⁰¹ and R¹⁰² are independently of each other C₁-C₁₈alkyl,substituted or unsubstituted C₆-C₁₈aryl, and Ar¹ and Ar² are eachindependently of each other a substituted or unsubstituted arylene, orheteroarylene group. Examples of substituted or unsubstituted arylene,or heteroarylene groups are divalent groups selected from substituted orunsubstituted benzene group, a substituted or unsubstituted naphthalenegroup, a substituted or unsubstituted anthracene group, a substituted orunsubstituted diphenylanthracene group, a substituted or unsubstitutedphenanthrene group, a substituted or unsubstituted acenaphthene group, asubstituted or unsubstituted biphenyl group, a substituted orunsubstituted fluorene group, a substituted or unsubstituted carbazolylgroup, a substituted or unsubstituted thiophene group, a substituted orunsubstituted triazole group and a substituted or unsubstitutedthiadiazole group.

The polymers of the present invention should have a glass transitiontemperature above 100° C., especially a glass transition temperatureabove 150° C.

R¹ and R² as well as R³ and R⁴ can be different from each other, but arepreferably the same. Most preferred R¹, R², R³ and R⁴ have the samemeaning.

R¹, R², R³ and R⁴ are preferably selected from C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D; C₁-C₁₈alkoxy,C₁-C₁₈alkoxy, which is substituted by E and/or interrupted by D;C₁-C₁₈perfluoroalkyl and are most preferred an optionally substitutedC₆-C₂₄aryl, or C₂-C₂₀heteroaryl group.

In a preferred embodiment of the present invention at least one, veryespecially at least two of R¹, R², R³ and R⁴ are different from H. Mostpreferred all of the substituents R¹, R², R³ and R⁴ are different fromH. In another preferred embodiment of the present invention at leastone, preferably two of the substituents R¹, R², R³ and R⁴ are anoptionally substituted C₁-C₁₈alkoxy group. Most preferred all of thesubstituents R¹, R², R³ and R⁴ are an optionally substitutedC₁-C₁₈alkoxy group.

Preferably, the polymer of the present invention comprises repeatingunit(s) of formula I, wherein R¹, R², R³ and R⁴ are independently ofeach other H, F, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by Eand/or interrupted by D, C₁-C₁₈ perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄arylwhich is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G; each group R⁵ and R⁶ is independently of each other ineach occurrence H, halogen, especially F, C₁-C₁₈alkyl, C₁-C₁₈alkyl whichis substituted by E and/or interrupted by D, C₁-C₁₈ perfluoroalkyl,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀ heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, C₇-C₂₅aralkyl, CN, or —CO—R²⁸,

m is 0, or an integer 1, or 2,

D is —CO—; —COO—; —S—; —SO—; —SO₂—; —O—; —NR²⁵—; —SiR³⁰R³¹—; —POR³²—;—CR²³═CR²⁴—; or —C≡C—; and

E is —OR²⁹; —SR²⁹; —NR²⁵R²⁶; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁶; —OCN; orhalogen, especially F;

G is E, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is interrupted by D, C₁-C₁₈perfluoroalkyl, C₁-C₁₈alkoxy, or C₁-C₈ alkoxy which is substituted by Eand/or interrupted by D,

R²³, R²⁴, R²⁵ and R²⁶ are independently of each other H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—;

R²⁷ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; especially C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—,

R²⁸ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,

R²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl,or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by—O—,

R³⁰ and R³¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, orC₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, and

R³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl.

Especially at least one, very especially at least two of R¹, R², R³ andR⁴ are different from H.

In an especially preferred embodiment the polymers contain repeatingunits of formula

wherein R¹, R², R³ and R⁴ are independently of each other C₆-C₁₂aryl, orC₂-C₁₁heteroaryl, which may optionally be substituted by one or moregroups G, wherein G is as defined above, or R¹, R², R³ and R⁴ areindependently of each other C₁-C₁₈alkyl, C₁-C₁₈alkyl which isinterrupted by —O—, C₁-C₁₈alkoxy; or C₁-C₁₈alkoxy which is interruptedby —O—. Preferably, R¹, R², R³ and R⁴ have the same meaning. Morepreferred R³ and R⁴ have the same meaning and are C₁-C₁₈alkoxy; orC₁-C₁₈alkoxy, which is interrupted by —O—.

In another preferred embodiment of the present invention polymers offormula Ia are preferred, wherein R¹, R², R³ and R⁴ are independently ofeach other

wherein n₃ is 0, or an integer 1, 2, 3, 4, or 5, R⁴ can be same, ordifferent in each occurrence and is C₁-C₂₅alkyl, or C₁-C₂₅alkoxy, or R¹,R², R³ and R⁴ are independently of each other C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is interrupted by —O—, C₁-C₁₈alkoxy; or C₁-C₁₈alkoxy which isinterrupted by —O—; especially C₁-C₁₈alkyl which is interrupted by —O—,C₁-C₁₈alkoxy; or C₁-C₁₈alkoxy which is interrupted by —O—. Preferably,R¹, R², R³ and R⁴ have the same meaning.

Preferably, R⁵ and R⁶ are independently of each other H, C₁-C₁₈alkyl,such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl,sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl,2-ethylhexyl, or n-heptyl; C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, such as —CH₂OCH₃, —CH₂OCH₂CH₃, —CH₂OCH₂CH₂OCH₃, or—CH₂OCH₂CH₂OCH₂CH₃; C₁-C₁₈alkoxy, such as methoxy, ethoxy, n-propoxy,iso-propoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, 2-methylbutoxy,n-pentyloxy, isopentyloxy, n-hexyloxy, 2-ethylhexyloxy, or n-heptyloxy;C₆-C₁₄aryl, such as phenyl, naphthyl, or biphenylyl, C₅-C₁₂cycloalkyl,such as cyclohexyl, C₆-C₁₄aryl which is substituted by G, such as—C₆H₄OCH₃, —C₆H₄OCH₂CH₃, —C₆H₃(OCH₃)₂, or —C₆H₃(OCH₂CH₃)₂, —C₆H₄—CH₃,—C₆H₃(CH₃)₂, —C₆H₂(CH₃)₃, —C₆H₄OtBu, or —C₆H₄tBu. Most preferred R⁵ andR⁶ are H.

m is preferably 0. If more than one group R⁵, or R⁶ is present withinone molecule, they can have different meanings.

D is preferably —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR²⁵—, wherein R²⁵is C₁-C₁₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, or sec-butyl, or C₆-C₁₄aryl, such as phenyl, naphthyl, orbiphenylyl.

E is preferably —OR²⁹; —SR²⁹; —NR²⁵R²⁵; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁵; or—CN; wherein R²⁵, R²⁷, R²⁸ and R²⁹ are independently of each otherC₁-C₁₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C₆-C₁₄aryl, suchas phenyl, naphthyl, or biphenylyl.

G has the same preferences as E, or is C₁-C₁₈alkyl, especiallyC₁-C₁₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, hexyl, octyl, 1-(2-hexyl)-decane, or 2-ethyl-hexyl.

Examples of especially preferred polymers, comprising repeating unit(s)of formula (Ia) are compounds A-1 to A-34 as described in claim 5.

The monomers for the preparation of the polymers of the presentinvention are new and form a further embodiment of the presentinvention. Accordingly, the present invention is also directed tomonomers of the formula

wherein Ar¹, Ar², n₁, n₂, R¹, R², R³, R⁴, R⁵, R⁶ and m are as definedabove. X¹¹ is independently in each occurrence a halogen atom,especially I, Cl, or Br; —ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ andR²⁰⁹ are identical or different and are H or C₁-C₆alkyl, wherein tworadicals optionally form a common ring and these radicals are optionallybranched or unbranched and X¹² is a halogen atom, very especially I, orBr; or —OS(O)₂CF₃, —OS(O)₂-aryl, especially

—OS(O)₂CH₃, —B(OH)₂, —B(OY¹¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y¹² is independently in each occurrence aC₂-C₁₀alkylene group, such as —CY¹³Y¹⁴—CY¹⁵Y¹⁶—, or—CY¹⁷Y¹⁸—CY¹⁹Y²⁰—CY²¹Y²²—, wherein Y¹³, Y¹⁴, Y¹⁵, Y¹⁶, Y¹⁷, Y¹⁸, Y¹⁹,Y²⁰, Y²¹ and Y²² are independently of each other hydrogen, or aC₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, or —C(CH₃)₂CH₂C(CH₃)₂—,

The compounds of formula

are new and form a further embodiment of the present invention.Accordingly, the present invention is also directed compounds of theformula XIV, wherein X¹¹, Ar¹, Ar², n₁, n₂, R⁵, R⁶ and m are as definedabove.

2,7-Dibromo-pyrene-4,5,9,10-tetraones of formula XIVa (n₁=n₂=0; X¹=Br)can be produced by reacting 2,7-di-tert-butyl-pyrene-4,5,9,10-tetraonesof formula XV or pyrene-4,5,9,10-tetraones of formula XII with Br₂/Feand NBS/H₂SO₄, respectively.

Pyrene-4,5,9,10-tetraones of formula XII can be produced by oxidizingpyrenes of formula XVI with sodium perchlorate or sodium periodate inthe presence of ruthenium trichlorate in methylenechlorid according tothe procedure described in J. Org. Chem. 2005, 70, 707-708.

Alternatively, 2,7-Dibromo-pyrene-4,5,9,10-tetraones of formula XIVa(n₁=n₂=0; X¹¹=Br) can be prepared by oxidizing pyrenes of formula XVIIwith sodium perchlorate or sodium periodate in the presence of rutheniumtrichlorate in methylenechlorid according to the procedure described inJ. Org. Chem. 2005, 70, 707-708. The synthesis of 2,7-dibromopyrene is,for example, described in J. Org. Chem. 1986, 51, 2847.

The monomers of formula XIa (n₁=n₂=0) can be reacted by known proceduresor in analogy to known procedures to monomers of formula XIb (n₁=n₂≠0):

-   -   Example 22a of WO04039786:

-   -   J. Org. Chem. 2007, 72, 2279:

2,7-Dibromo-pyrene-4,5,9,10-tetraones of formula XIVa (n₁=n₂=0; X¹¹=Br)can be reacted to monomers of formula XI (n₁=n₂=0; X¹¹=Br) by knownprocedures or in analogy to known procedures:

-   -   WO2005/104264 (R¹=alkyl and aryl):

-   -   Org. Lett. 10 (2008) 773:

Alternatively, monomers of formula XI can be obtained by reactingcompounds of formula XIII with bis(tricyclohexyltin)sulphide, or B₂S₃.Reference is, for example, made to US20070191583 and Macromolecules 39(2006) 5213-5221. The synthesis of compounds of formula XIII can be doneaccording to, or in analogy to procedures described therein.

In one embodiment, the polymers according to the invention consist onlyof one or more type of repeating units of formula I. In a preferredembodiment, the polymers according to the invention consist of preciselyone type of repeating unit of formula I (homopolymers).

According to the present invention the term “polymer” comprises polymersas well as oligomers, wherein a polymer is a molecule of high relativemolecular mass, the structure of which essentially comprises therepetition of units derived, actually or conceptually, from molecules oflow relative molecular mass and an oligomer is a molecule ofintermediate molecular mass, the structure of which essentiallycomprises a small plurality of units derived, actually or conceptually,from molecules of lower relative molecular mass. A molecule is regardedas having a high relative molecular mass if it has properties which donot vary significantly with the removal of one or a few of the units. Amolecule is regarded as having an intermediate molecular mass if it hasproperties which do vary significantly with the removal of one or a fewof the units.

According to the present invention a homopolymer is a polymer derivedfrom one species of (real, implicit, or hypothetical) monomer. Manypolymers are made by the mutual reaction of complementary monomers.These monomers can readily be visualized as reacting to give an“implicit monomer”, the homopolymerisation of which would give theactual product, which can be regarded as a homopolymer. Some polymersare obtained by chemical modification of other polymers, such that thestructure of the macromolecules that constitute the resulting polymercan be thought of having been formed by the homopolymerisation of ahypothetical monomer.

Accordingly a copolymer is a polymer derived from more than one speciesof monomer, e.g. bipolymer, terpolymer, quaterpolymer, etc.

The oligomers of this invention have a weight average molecular weightof <2,000 Daltons. The polymers of this invention preferably have aweight average molecular weight of 2,000 Daltons or greater, especially2,000 to 2,000,000 Daltons, more preferably 10,000 to 1,000,000 and mostpreferably 20,000 to 500,000 Daltons. Molecular weights are determinedaccording to gel permeation chromatography using polystyrene standards.

The present invention is illustrated in more detail on the basis of anespecially preferred embodiment below, but should not be limitedthereto. In said embodiment the polymer is a polymer of formula

wherein Ar¹, n₁, Ar², n₂, R¹, R², R³, R⁴, R⁵, R⁶ and m are as definedabove, T and Ar³ are as defined in WO06/097419, wherein Ar³ can also bea repeating unit of formula

especially

as described in WO06/097419, and/or

especially

as described in WO08/012,250, wherein R^(1″), R^(2″) and R^(3″) areindependently of each other C₆-C₁₂aryl, or C₂-C₁₁heteroaryl, which mayoptionally be substituted by one or more groups G, wherein G is asdefined above, and R^(4″) has the meaning of R^(3″), or is C₁-C₁₈alkyl,especially C₄-C₁₈alkyl,

R^(7′) is an organic substituent, wherein two or more substituentsR^(7′) in the same molecule may have different meanings, or can formtogether an aromatic, or heteroaromatic ring, or ring system, and

x′ is 0, or an integer of 1 to 5.

A is a 5-, 6-, or 7-membered heteroaromatic ring, containing oneheteroatom selected from nitrogen, oxygen and sulphur, which can besubstituted and/or can be part of a fused aromatic or heteroaromaticring system,

R^(1′) and R^(4′) are hydrogen,

R^(2′), R^(3′), R^(5′) and R^(6′) are independently of each other H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is interrupted by D, C₁-C₁₈perfluoroalkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is interrupted by D,C₇-C₂₅aralkyl, or a group —X²—R^(18′),

R^(8′) and R^(9′) are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is interrupted by D, C₁-C₁₈ perfluoroalkyl,C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is interrupted by D, or a group—X²—R^(18′), or two substituents R^(2′) and R^(3′) and/or R^(5′) andR^(6′), which are adjacent to each other,

together form a group

or two substituents R^(5′) and R^(3′), which are adjacent to each other,together form a group

orR^(8′) and R^(9′) together form a group

wherein R^(205′), R^(206′), R^(207′), R^(208′), R^(209′) and R^(210′)are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₁-C₁₈alkoxy, or C₁-C₁₈alkoxywhich is substituted by E and/or interrupted by D, C₁-C₁₈perfluoroalkyl,

R^(10′) is H, C₆-C₁₈aryl, which can be substituted by G,C₂-C₁₉heteroaryl, which can be substituted by G, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is interrupted by D, C₁-C₁₈ perfluoroalkyl,C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interruptedby D, or a group —X²—R^(18′), wherein X² is a spacer, such asC₆-C₁₂aryl, or C₆-C₁₂heteroaryl, especially phenyl, or naphthyl, whichcan be substituted one more, especially one to two times withC₁-C₁₈alkyl, C₁-C₁₈alkyl which is interrupted by D, C₁-C₁₈perfluoroalkyl, C₁-C₁₈alkoxy, or C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, and R^(18′) is H, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is interrupted by D, C₁-C₁₈ perfluoroalkyl, C₁-C₁₈ alkoxy,C₁-C₁₈alkoxy which is interrupted by D, or —NR^(25′)R^(26′);

X′ is O, S, or NR^(17′),

R^(11′) and R^(14′) are hydrogen,

R^(12′), R^(13′), R^(15′) and R^(16′) are hydrogen,

R^(17′) is C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl,C₁-C₁₈ perfluoroalkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkylwhich is interrupted by —O—; or

two substituents R^(11′) and R^(12′), and/or R^(14′) and R^(16′),R^(12′) and R^(13′), and/or R^(15′) and R^(16′), which are adjacent toeach other, together form a group

or two substituents R^(15′) and R^(13′), which are adjacent to eachother, together form a group

wherein R^(105′), R^(106′), R^(107′) and R^(108′) are independently ofeach other H, or C₁-C₈alkyl, D, E and G are as defined above;

a is 1,

b is 0, or 1,

c is 0.005 to 1,

d is 0, or 1,

e is 0, or 1, wherein e is not 1, if d is 0,

f is 0.995 to 0, wherein the sum of c and f is 1.

Ar³ is preferably selected from repeating units of formula:

wherein

R⁴⁴ and R⁴¹ are hydrogen, C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, and

R⁴⁵ is H, C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, especially C₁-C₁₈alkyl which is interrupted by —O—,

R¹¹⁶ and R¹¹⁷ are independently of each other H, halogen, —CN,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, C₇-C₂₅aralkyl, —C(═O)—R¹²⁷, —C(═O)OR¹²⁷, or—C(═O)NR¹²⁷R¹²⁶,

R¹¹⁹ and R¹²⁰ are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, or C₇-C₂₅aralkyl, or

R¹¹⁹ and R¹²⁰ together form a group of formula ═CR¹²¹R¹²², wherein

R¹²¹ and R¹²² are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂-C₂₀heteroaryl,or C₂-C₂₀heteroaryl which is substituted by G, or

R¹¹⁹ and R¹²⁰ together form a five or six membered ring, whichoptionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,C₇-C₂₅aralkyl, or —C(═O)—R¹²⁷, and

R¹²⁶ and R¹²⁷ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—,

wherein G, D and E are as defined above.

The repeating units T are in particular selected from the followinggroup VI:

especially

wherein

X¹ is a hydrogen atom, or a cyano group,

R¹¹⁶ and R¹¹⁷ are as defined above,

R⁴¹ can be the same or different at each occurrence and is Cl, F, CN,N(R⁴⁵)₂, a C₁-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, a C₁-C₂₅alkoxygroup, in which one or more carbon atoms which are not in neighborhoodto each other could be replaced by —NR⁴⁵—, —O—, —S—, —C(═O)—O—, or—O—C(═O)—O—, and/or wherein one or more hydrogen atoms can be replacedby F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein one or morecarbon atoms can be replaced by O, S, or N, and/or which can besubstituted by one or more non-aromatic groups R⁴¹, or two or moregroups R⁴¹ form a ring system;

R⁴⁵ is H, a C₁-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, in which one ormore carbon atoms which are not in neighborhood to each other could bereplaced by —NR⁴⁵—, —O—, —S—, —C(═O)—O—, or, —O—C(═O)—O—, and/or whereinone or more hydrogen atoms can be replaced by F, a C₆-C₂₄aryl group, ora C₆-C₂₄aryloxy group, wherein one or more carbon atoms can be replacedby O, S, or N, and/or which can be substituted by one or morenon-aromatic groups R⁴¹,

R^(45′) is H, a C₁-C₂₅alkyl group, or a C₄-C₁₈cycloalkyl group,

n can be the same or different at each occurrence and is 0, 1, 2, or 3,especially 0, 1, or 2, very especially 0 or 1, and u is 1, 2, 3, or 4;

A⁴ is a C₆-C₂₄aryl group, a C₂-C₃₀heteroaryl group, especially phenyl,naphthyl, anthryl, biphenylyl, 2-fluorenyl, phenanthryl, or perylenyl,which can be substituted by one or more non-aromatic groups R⁴¹, whereinT is preferably a repeating unit of formula VIa, VIb or VIf.Homopolymers of formula VII, wherein a=1, b=0, c=1, d=0, e=0, f=0, are,for example, obtained by nickel coupling reactions, especially theYamamoto reaction:

wherein Ar¹, n₁, Ar², n₂, R¹, R², R³, R⁴, R⁵, R⁶ and m are as definedabove. In said aspect homopolymers consisting of repeating units offormula Ia are preferred.

Copolymers of formula VII, involving repeating units of formula I and—Ar³— (a=1, c=0.995 to 0.005, b=0, d=1, e=0, f=0.005 to 0.995), can beobtained by nickel coupling reactions:

wherein X¹⁰ is a repeating unit of formula I, especially Ia, c, f andAr³ are as defined above.

Polymerization processes involving only dihalo-functional reactants maybe carried out using nickel coupling reactions. One such couplingreaction was described by Colon et al. in J. Pol. Sci., Part A, PolymerChemistry Edition 28 (1990) 367, and by Colon et al. in J. Org. Chem. 51(1986) 2627. The reaction is typically conducted in a polar aproticsolvent (e.g., dimethylacetamide) with a catalytic amount of nickelsalt, a substantial amount of triphenylphosphine and a large excess ofzinc dust. A variant of this process is described by loyda et al. inBull. Chem. Soc. Jpn, 63 (1990) 80 wherein an organo-soluble iodide wasused as an accelerator.

Another nickel-coupling reaction was disclosed by Yamamoto in Progressin Polymer Science 17 (1992) 1153 wherein a mixture of dihaloaromaticcompounds was treated with an excess amount of nickel(1,5-cyclooctadiene) complex in an inert solvent. All nickel-couplingreactions when applied to reactant mixtures of two or more aromaticdihalides yield essentially random copolymers. Such polymerizationreactions may be terminated by the addition of small amounts of water tothe polymerization reaction mixture, which will replace the terminalhalogen groups with hydrogen groups. Alternatively, a monofunctionalaryl halide may be used as a chain-terminator in such reactions, whichwill result in the formation of a terminal aryl group.

Nickel-coupling polymerizations yield essentially homopolymers or randomcopolymers comprising units of formula I and units derived from otherco-monomers.

Homopolymers of formula VII, wherein a=1, c=1, b=0, d=1, e=0, f=1, canbe obtained, for example, by the Suzuki reaction:

wherein X¹⁰ and Ar³ are as defined above.

The condensation reaction of an aromatic boronate and a halogenide,especially a bromide, commonly referred to as the “Suzuki reaction”, istolerant of the presence of a variety of organic functional groups asreported by N. Miyaua and A. Suzuki in Chemical Reviews, Vol. 95, pp.457-2483 (1995). This reaction can be applied to preparing highmolecular weight polymers and copolymers. Preferred catalysts are2-dicyclohexylphosphino-2′,6′-di-alkoxybiphenyl/palladium(II)acetates.An especially preferred catalyst is2-dicyclohexylphosphino-2′,6′-di-methoxybiphenyl(sPhos)/palladium(II)acetate.

To prepare polymers corresponding to formula VIIc, a dihalogenide, suchas a dibromide or dichloride, especially a dibromide corresponding toformula Br—X¹⁰Br is reacted with an equimolar amount of a diboronic acidor diboronate corresponding to formula

wherein X¹¹ is independently in each occurrence —B(OH)₂, —B(OY¹)₂ or

wherein Y¹¹ is independently in each occurrence a C₁-C₁₀alkyl group andY¹² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY¹³Y¹⁴—CY¹⁵Y¹⁶—, or —CY¹⁷Y¹⁸—CY¹⁹Y²⁰—CY²¹Y²²—, wherein Y¹³, Y¹⁴, Y¹⁵,Y¹⁶, Y¹⁷, Y¹⁸, Y¹⁹, Y²⁰, Y²¹ and Y²² are independently of each otherhydrogen, or a C₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, or—C(CH₃)₂CH₂C(CH₃)₂—, under the catalytic action of Pd and a phosphineligand, especially triphenylphosphine. The reaction is typicallyconducted at about 70° C. to 180° C. in an aromatic hydrocarbon solventsuch as toluene. Other solvents such as dimethylformamide andtetrahydrofuran can also be used alone, or in mixtures with an aromatichydrocarbon. An aqueous base, preferably sodium carbonate, potassiumcarbonate, K₃PO₄, or bicarbonate, is used as the HBr scavenger.Depending on the reactivities of the reactants, a polymerizationreaction may take 2 to 100 hours. Organic bases, such as, for example,tetraalkylammonium hydroxide, and phase transfer catalysts, such as, forexample TBAB, can promote the activity of the boron (see, for example,Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 andreferences cited therein). Other variations of reaction conditions aregiven by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994)5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol. RapidCommun. 17 (1996) 239-252.

If desired, a monofunctional aryl halide or aryl boronate may be used asa chain-terminator in such reactions, which will result in the formationof a terminal aryl group.

It is possible to control the sequencing of the monomeric units in theresulting copolymer by controlling the order and composition of monomerfeeds in the Suzuki reaction.

Homopolymers of formula VII, wherein a=1, c=1, b=1, d=0, e=0, f=0, canbe obtained, for example by the Heck reaction:

wherein X¹⁰ and T are as defined above.

Polyphenylenethenylene derivatives and polyphenylenethynylenederivatives can be obtained by polymerization of divinyl or diethinylcompounds with dihalogen compounds by the Heck reaction (R. F. Heck,Palladium Reagents in Organic Synthesis, Academic Press, New York 1985,pp. 179; L. S. Hegedus, Organometalics in Synthesis, Ed. M. Schlosser,Wiley, Chichester, UK 1994, pp. 383; Z. Bao, Y. Chen, R. Cai, L. Yu,Macromolecules 26 (1993) pp. 5281; W.-K. Chan, L. Yu, Macromolecules 28(1995) pp. 6410; A. Hilberer, H.-J. Brouwer, B.-J. van der Scheer, J.Wildeman, G. Hadziioannou, Macromolecules 1995, 28, 4525) and theSonogaschira reaction (Dmitri Gelman and Stephen L. Buchwald, Angew.Chem. Int. Ed. 42 (2003) 5993-5996; Rik R. Tykwinski, Angew. Chem. 115(2003) 1604-1606; Jason M. Nolan and Daniel L. Comins, J. Org. Chem. 68(2003) 3736-3738; Jiang Cheng et al., J. Org. Chem. 69 (2004) 5428-5432;Zolta'n Nova'k et al., Tetrahedron 59 (2003) 7509-7513):

The Sonogashira reaction is done in the presence a copper (I) catalyst,and/or palladium(0), such as, for example, tetrakis(triphenyl-phosphine)palladium(0), optionally in a solvent, such as toluene, dimethylformamide, or dimethyl sulfoxide, and optionally a base, such as sodiumhydride, potassium carbonate, sodium carbonate, or an amine base, suchas piperidine. With special palladium catalysts the copper catalyst isnot required (Angew. Chem. 2007, 119, 850-888). The reaction time andtemperature depends on the starting materials and reaction conditions.Usually the dibromo-compound is reacted with the alkine at a temperatureof from 50° C. to 100° C., especially 60 to 80° C. for 1 h to 48 hhours. This reaction, referred to as an Sonogashira reaction(Pd/Cu-catalyzed cross-coupling of organohalides with terminal alkynes),Cadiot-Chodkiewicz coupling or Castro-Stephens reaction (theCastro-Stephens coupling uses stoichiometric copper, whereas theSonogashira variant uses catalytic palladium and copper), is describedby Sonogashira K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 4467;Richard Heck (discovered the same transformation using palladium butwithout the use of copper) J. Organomet. Chem. 1975, 93, 259; McCrindle,R.; Ferguson, G.; Arsenaut, G. J.; McAlees, A. J.; Stephenson, D. K. J.Chem. Res. (S) 1984, 360; Sakamoto, T.; Nagano, T.; Kondo, Y.; Yamanaka,H. Chem. Pharm. Bull. 1988, 36, 2248; Rossi, R. Carpita, A.; Belina, F.Org. Prep. Proc. Int. 1995, 27, 129; Ernst, A.; Gobbi, L.; Vasella, A.Tetrahedron Lett. 1996, 37, 7959; Campbell, I. B. In OrganocopperReagents; Taylor, R. J. K. Ed.; IRL Press: Oxford, UK, 1994, 217.(Review); Hundermark, T.; Littke, A.; Buchwald, S. L.; Fu, G. C. Org.Lett. 2000, 2, 1729; Dai, W.-M.; Wu, A. Tetrahedron Lett. 2001, 42, 81;Alami, M.; Crousse, B.; Ferri, F. J. Organomet. Chem. 2001, 624, 114;Bates, R. W.; Boonsombat, J. J. Chem. Soc., Perkin Trans. 1 2001, 654;Batey, R. A.; Shen, M.; Lough, A. J. Org. Lett. 2002, 4, 1411; Balova,I. A.; Morozkina, S, N.; Knight, D. W.; Vasilevsky, S. F. TetrahedronLett. 2003, 44, 107; Garcia, D.; Cuadro, A. M.; Alvarez-Builla, J.;Vaquero, J. J. Org. Lett. 2004, 6, 4175; Li, P.; Wang, L.; Li, H.Tetrahedron 2005, 61, 8633, Lemhadri, M.; Doucet, H.; Santelli, M.Tetrahedron 2005, 61, 9839, Angew. Chem. 2007, 119, 8632-8635, Angew.Chem. 2006, 118, 6335-6339, J. Am. Chem. Soc. 2005, 127, 9332-9333, andAdv. Mater. 2007, 19, 1234-1238.

(Random) copolymers of formula VII, wherein a is 1, b is 1, c is 0.005to 0.995, d is 1, e is 1, f is 0.995 to 0.005, wherein the sum of c andf is 1, can also be obtained by the Heck reaction:

wherein a, b, c, d, e, f, X¹⁰, Ar³ and T are as defined above.

The polymers containing groups of formulas (I) may be prepared by anysuitable process, but are preferably prepared by the processes describedabove.

The polymers of the present invention can optionally comprise endmoieties E¹, wherein E¹ is an aryl moiety which may optionally besubstituted with a reactive group capable of undergoing chain extensionor crosslinking, or a tri(C₁-C₁₈)alkylsiloxy group. As used herein, areactive group capable of undergoing chain extension or crosslinkingrefers to any group which is capable of reacting with another of thesame group or another group so as to form a link to prepare polymers.Preferably, such reactive group is a hydroxy, glycidyl ether, acrylateester, methacrylate ester, ethenyl, ethynyl, maleimide, naphthimide,oxetane, trifluorovinyl ether moiety or a cyclobutene moiety fused tothe aromatic ring of E¹.

The polymers of the present invention, where E¹ are reactive groups asdefined above, are capable of crosslinking to form solvent resistant,heat-resistant films at 100° C. or more, more preferably at 150° C. ormore. Preferably, such crosslinking occurs at 350° C. or less, morepreferably 300° C. or less and most preferably 250° C. or less. Thecrosslinkable polymers of the invention are stable at 100° C. or moreand more preferably 150° C. or more. “Stable” as used herein means thatsuch polymers do not undergo crosslinking or polymerization reactions ator below the stated temperatures. If a crosslinkable material isdesired, E¹ is preferably a vinylphenyl, an ethynylphenyl, or 4-(or3-)benzocyclobutenyl radical. In another embodiment, E¹ is selected froma group of phenolic derivatives of the formula —C₆H₄—O—Y, wherein Y is

If desired, the cross-linkable groups can be present in other parts ofthe polymer chain. For example, one of the substituents of theco-monomer T may be a crosslinkable group E¹.

The end-capping agent E¹-X¹² (E¹ is as defined above and X¹² is eitherCl or Br) is incorporated into the polymers of the present inventionunder the condition in which the resulting polymers are substantiallycapped by the reactive group E¹. The reactions useful for this purposeare the nickel-coupling, Heck reactions and Suzuki reactions describedabove. The average degree of polymerization is controlled by the moleratio of monomers to end-capping agent.

The polymers according to the invention can be worked up by knownmethods which are familiar to the person skilled in the art, asdescribed, for example, in D. Braun, H. Cherdron, H. Ritter, Praktikumder makromolekularen Stoffe, 1^(st) Edn., Wiley VCH, Weinheim 1999, p.68-79 or R. J. Young, P. A. Lovell, Introduction to Polymers, Chapman &Hall, London 1991. For example, the reaction mixture can be filtered,diluted with aqueous acid, extracted and the crude product obtainedafter drying and stripping-off of the solvent can be further purified byreprecipitation from suitable solvents with addition of precipitants.Residual palladium can be removed by using activated carbon,chromatography etc. Advantageously, the residual palladium could bereduced to <3 ppm by washing the crude organic solvent layer containingthe polymer with an aqueous solution of L-cysteine at room temperatureto the boiling point of the organic solvent, especially by washing atoluene layer containing the polymer with an aqueous solution ofL-cysteine at 85 to 90° C., optionally followed by washing with asolution of L-cysteine and sodium thiosulfate at 78 to 82° C. (MahavirPrashad, Yugang Liu, Oljan Repicoe, Adv. Synth. Catal. 2003, 345,533-536; Christine E. Garrett, Kapa Prasad, Adv. Synth. Catal. 2004,346, 889-900). Additionally the Pd can be removed by washing the polymerwith an aqueous NaCN solution as described in U.S. Pat. No. 6,956,095.Polymer-analogous reactions can subsequently be carried out for furtherfunctionalization of the polymer. Thus, for example, terminal halogenatoms can be removed reductively by reduction with, for example, LiAlH₄(see, for example, J. March, Advanced Organic Chemistry, 3^(rd) Edn.McGraw-Hill, p. 510).

Another aspect of this invention is related to polymer blends containing1 to 99 percent of at least one containing polymers comprising a unit offormula I. The remainder 1 to 99 percent of the blend is composed of oneor more polymeric materials selected from among chain growth polymerssuch as polystyrene, polybutadiene, poly(methyl methacrylate), andpoly(ethylene oxide); step-growth polymers such as phenoxy resins,polycarbonates, polyamides, polyesters, polyurethanes, and polyimides;and crosslinked polymers such as crosslinked epoxy resins, crosslinkedphenolic resins, crosslinked acrylate resins, and crosslinked urethaneresins. Examples of these polymers may be found in Preparative Methodsof Polymer Chemistry, W. R. Sorenson and T. W. Campbell, Second Edition,Interscience Publishers (1968). Also may be used in the blends areconjugated polymers such as poly(phenylene vinylene), substitutedpoly(phenylene vinylene)s, substituted polyphenylenes andpolythiophenes. Examples of these conjugated polymers are given byGreenham and Friend in Solid State Physics, Vol. 49, pp. 1-149 (1995).

In an especially preferred embodiment the present invention is directedto polymers of formula

wherein R¹, R², R³ and R⁴ are independently of each other

wherein n₃ is 0, or an integer 1, 2, or 3, especially 0, or 1; and R¹¹can be the same or different in each occurrence and is H, C₁-C₂₅alkyl,which can be optionally interrupted by O, or C₁-C₂₅alkoxy, which can beoptionally interrupted by O, and

Ar^(3′) is

wherein

R^(1″), R^(2″) and R^(3″) are independently of each other

wherein n_(1′) is 0, or an integer 1, 2, 3, or 4, especially 0, 1, or 2;n_(2′) is 0, or an integer 1, 2, or 3, especially 0, 1, or 2; n₃, is 0,or an integer 1, 2, 3, 4, or 5, especially 0, 1, 2, or 3; and R^(10″)and R^(11″) are independently of each other C₁-C₂₅alkyl, orC₁-C₂₅alkoxy, and R^(4″) has the meaning of R^(3″), or is C₁-C₁₈alkyl,especially C₄-C₁₈alkyl,

R⁴⁴, R¹¹⁶, R¹¹⁷, R¹¹⁹ and R¹²⁰ are as defined above,

R^(8′) and R^(9′) are independently of each other

wherein n₃ and R¹¹ are as defined above, R^(17′) is C₁-C₂₅alkyl, whichcan be optionally interrupted by O, and

R^(10′) is R^(8′), or

wherein n₂ is 0, 1, or 2.

R^(1″), R^(2″) and R^(3″) are preferably independently of each other

R^(4″) has the meaning of R^(3″), or is C₁-C₁₈alkyl, especiallyC₄-C₁₈alkyl.

The following polymers are especially preferred:

The polymers of the present invention can show high photoluminescenceand/or electroluminescence.

Halogen is fluorine, chlorine, bromine and iodine.

C₁-C₂₅alkyl (C₁-C₁₈alkyl) is typically linear or branched, wherepossible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl,1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl.C₁-C₈alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl. C₁-C₄alkyl is typicallymethyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,tert.-butyl.

C₁-C₂₅alkoxy(C₁-C₁₈alkoxy) groups are straight-chain or branched alkoxygroups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy,octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy,tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy andoctadecyloxy. Examples of C₁-C₄alkoxy are methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy,2-pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy,n-octyloxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexyloxy. Examples ofC₁-C₄alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec.-butoxy, isobutoxy, tert.-butoxy. The term “alkylthio group” meansthe same groups as the alkoxy groups, except that the oxygen atom of theether linkage is replaced by a sulfur atom.

C₂-C₂₅alkenyl (C₂-C₁₈alkenyl) groups are straight-chain or branchedalkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl,2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl,3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl,n-dodec-2-enyl or n-octadec-4-enyl.

C₂₋₂₄alkynyl (C₂₋₁₈alkynyl) is straight-chain or branched and preferablyC₂₋₈alkynyl, which may be unsubstituted or substituted, such as, forexample, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl,2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl,1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl,trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl,1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

C₁-C₁₈ perfluoroalkyl, especially C₁-C₄ perfluoroalkyl, is a branched orunbranched radical such as for example —CF₃, —CF₂CF₃, —CF₂CF₂CF₃,—CF(CF₃)₂, —(CF₂)₃CF₃, and —C(CF₃)₃.

The terms “haloalkyl, haloalkenyl and haloalkynyl” mean groups given bypartially or wholly substituting the above-mentioned alkyl group,alkenyl group and alkynyl group with halogen, such as trifluoromethyletc. The “aldehyde group, ketone group, ester group, carbamoyl group andamino group” include those substituted by an alkyl group, a cycloalkylgroup, an aryl group, an aralkyl group or a heterocyclic group, whereinthe alkyl group, the cycloalkyl group, the aryl group, the aralkyl groupand the heterocyclic group may be unsubstituted or substituted. The term“silyl group” means a group of formula —SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³and R⁶⁴ are independently of each other a C₁-C₈alkyl group, inparticular a C₁-C₄ alkyl group, a C₆-C₂₄aryl group or a C₇-C₁₂aralkylgroup, such as a trimethylsilyl group.

The term “cycloalkyl group” is typically C₄-C₁₈cycloalkyl, especiallyC₅-C₁₂cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl,preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, whichmay be unsubstituted or substituted. The term “cycloalkenyl group” meansan unsaturated alicyclic hydrocarbon group containing one or more doublebonds, such as cyclopentenyl, cyclopentadienyl, cyclohexenyl and thelike, which may be unsubstituted or substituted. The cycloalkyl group,in particular a cyclohexyl group, can be condensed one or two times byphenyl which can be substituted one to three times with C₁-C₄-alkyl,halogen and cyano.

Examples of such condensed cyclohexyl groups are:

in particular

wherein R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵ and

R⁵⁶ are independently of each other C₁-C₈-alkyl, C₁-C₈-alkoxy, halogenand cyano, in particular hydrogen.

Aryl is usually C₆-C₃₀aryl, preferably C₆-C₂₄aryl (C₆-C₁₈aryl), whichoptionally can be substituted, such as, for example, phenyl,4-methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl,phenanthryl, anthryl, tetracyl, pentacyl, hexacyl, or quaderphenylyl,which may be unsubstituted or substituted.

The term “aralkyl group” is typically C₇-C₂₅aralkyl, such as benzyl,2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl,ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl,ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C₇-C₁₈aralkyl such asbenzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl,ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl orω-phenyl-octadecyl, and particularly preferred C₇-C₁₂aralkyl such asbenzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl,ω-phenyl-butyl, or ω,ω-dimethyl-ω-phenyl-butyl, in which both thealiphatic hydrocarbon group and aromatic hydrocarbon group may beunsubstituted or substituted.

The term “aryl ether group” is typically a C₆₋₂₄aryloxy group, that isto say O—C₆₋₂₄aryl, such as, for example, phenoxy or 4-methoxyphenyl.The term “aryl thioether group” is typically a C₆₋₂₄arylthio group, thatis to say S—C₆₋₂₄aryl, such as, for example, phenylthio or4-methoxyphenylthio. The term “carbamoyl group” is typically aC₁₋₁₈carbamoyl radical, preferably C₁₋₈-carbamoyl radical, which may beunsubstituted or substituted, such as, for example, carbamoyl,methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl,dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

The terms “aryl” and “alkyl” in alkylamino groups, dialkylamino groups,alkylarylamino groups, arylamino groups and diaryl groups are typicallyC₁-C₂₅alkyl and C₆-C₂₄aryl, respectively.

Alkylaryl refers to alkyl-substituted aryl radicals, especiallyC₇-C₁₂alkylaryl. Examples are tolyl, such as 3-methyl-, or4-methylphenyl, or xylyl, such as 3,4-dimethylphenyl, or3,5-dimethylphenyl.

Heteroaryl is typically C₂-C₂₆heteroaryl (C₂-C₂₀heteroaryl), i.e. a ringwith five to seven ring atoms or a condensed ring system, whereinnitrogen, oxygen or sulfur are the possible hetero atoms, and istypically an unsaturated heterocyclic group with five to 30 atoms havingat least six conjugated π-electrons such as thienyl, benzo[b]thienyl,dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl,benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl,imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl,pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl,purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl,naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl,carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl,acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl,phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, which can beunsubstituted or substituted.

Possible substituents of the above-mentioned groups are C₁-C₈alkyl, ahydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen,halo-C₁-C₈alkyl, a cyano group, an aldehyde group, a ketone group, acarboxyl group, an ester group, a carbamoyl group, an amino group, anitro group or a silyl group, especially C₁-C₈alkyl, C₁-C₈alkoxy,C₁-C₈alkylthio, halo-C₁-C₈alkyl, or a cyano group.

If a substituent, such as, for example R⁶ occurs more than one time in agroup, it can be different in each occurrence.

The wording “substituted by G” means that one, or more, especially oneto three substituents G might be present.

As described above, the aforementioned groups may be substituted by Eand/or, if desired, interrupted by D. Interruptions are of coursepossible only in the case of groups containing at least 2 carbon atomsconnected to one another by single bonds; C₆-C₁₈aryl is not interrupted;interrupted arylalkyl or alkylaryl contains the unit D in the alkylmoiety. C₁-C₁₈alkyl substituted by one or more E and/or interrupted byone or more units D is, for example, (CH₂CH₂O)₁₋₉—R^(x), where R^(x) isH or C₁-C₁₀alkyl or C₂-C₁₀alkanoyl (e.g. CO—CH(C₂H₅)C₄H₉),CH₂—CH(OR^(y′))—CH₂—O—R^(Y), where R^(Y) is C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, phenyl, C₇-C₁₅phenylalkyl, and R^(y′) embraces thesame definitions as R^(y′) or is H;

C₁-C₈alkylene-COO—R^(z), e.g. CH₂COOR^(z), CH(CH₃)COOR^(z),C(CH₃)₂COOR^(z), where R^(z) is H, C₁-C₁₈alkyl, (CH₂CH₂O)₁₋₉—R^(x), andR^(x) embraces the definitions indicated above; CH₂CH₂—O—CO—CH═CH₂;CH₂CH(OH)CH₂—O—CO—C(CH₃)═CH₂.

Preferred arylene radicals are 1,4-phenylene, 2,5-tolylene,1,4-naphthylene, 1,9 antracylene, 2,7-phenantrylene and2,7-dihydrophenantrylene.

Preferred heteroarylene radicals are 2,5-pyrazinylene,3,6-pyridazinylene, 2,5-pyridinylene, 2,5-pyrimidinylene,1,3,4-thiadiazol-2,5-ylene, 1,3-thiazol-2,4-ylene,1,3-thiazol-2,5-ylene, 2,4-thiophenylene, 2,5-thiophenylene,1,3-oxazol-2,4-ylene, 1,3-oxazol-2,5-ylene and1,3,4-oxadiazol-2,5-ylene, 2,5-indenylene and 2,6-indenylene.

Another aspect of the invention is the films formed from the polymers ofthe invention. Such films can be used in polymeric light-emitting diodes(PLEDs). Preferably, such films are used as emitting layers. These filmsmay also be used as protective coatings for electronic devices and asfluorescent coatings. The thickness of the coating or film is dependentupon the ultimate use. Generally, such thickness can be from 0.01 to 200microns. In that embodiment wherein the coating is used as a fluorescentcoating, the coating or film thickness is from 10 to 200 microns. Inthat embodiment where the coatings are used as electronic protectivelayers, the thickness of the coating can be from 5 to 20 microns. Inthat embodiment where the coatings are used in a polymericlight-emitting diode, the thickness of the layer formed is 0.01 to 0.5microns. The polymers of the invention form good pinhole- anddefect-free films. Such films can be prepared by means well known in theart including spin-coating, spray-coating, dip-coating androller-coating. Such coatings are prepared by a process comprisingapplying a composition to a substrate and exposing the appliedcomposition to conditions such that a film is formed. The conditionswhich form a film depend upon the application technique. Preferably, thesolution contains from 0.1 to 10 weight percent of the polymers. Thiscomposition is applied to the appropriate substrate by the desiredmethod and the solvent is allowed to evaporate. Residual solvent may beremoved by vacuum and/or by heat-drying. The films are preferablysubstantially uniform in thickness and substantially free of pinholes.In another embodiment, the polymers may be partially cured. This isknown as B-staging.

A further embodiment of the present invention is directed to anelectronic device or a component therefore, comprising a substrate and apolymer according to the present invention.

In such a device the polymers according to the present invention areused as electroluminescent material. For the purposes of the presentinvention, the term “electroluminescent material” is taken to meanmaterials which can be used as or in an active layer in anelectroluminescent device. The term “active layer” means that the layeris capable of emitting light (light-emitting layer) on application of anelectric field and/or that it improves the injection and/or transport ofthe positive and/or negative charges (charge injection or chargetransport layer). The invention therefore also relates to the use of thepolymers according to the invention as electroluminescent material. Theinvention furthermore relates to an electroluminescent material whichcomprises the polymers according to the invention. Electroluminescentdevices are used, for example, as self-illuminating display elements,such as control lamps, alphanumeric displays, signs and inopto-electronic couplers.

A device according to the present invention may be prepared inaccordance with the disclosure of WO99/48160, the contents of which areincorporated by reference. Polymers according to the present inventionmay be present in the device as the sole light emitting polymer or as acomponent in a blend further comprising hole and/or electrontransporting polymers. Alternatively, the device may comprise distinctlayers of a polymer of the present invention, a hole transportingpolymer and/or an electron transporting polymer.

In one embodiment the electronic device comprises an electroluminescentdevice, which comprises

(a) a charge injecting layer for injecting positive charge carriers,

(b) a charge injecting layer for injecting negative charge carriers,

(c) a light-emissive layer located between the layers (a) and (b)comprising a polymer according to the present invention.

The layer (a) may be a positive charge carrier transport layer which islocated between the light emissive layer (c) and an anode electrodelayer, or may be an anode electrode layer. The layer (b) may be anegative charge carrier transport layer which is located between thelight emissive layer (c) and an cathode electrode layer, or may be ancathode electrode layer. Optionally, an organic charge transport layercan be located between the light emissive layer (c) and one of thecharge carrier injecting layers (a) and (b).

The EL device emits light in the visible electro-magnetic spectrumbetween 400 nm and 780 nm, preferably between 430 nm and 470 nm for ablue color, preferably between 520 nm and 560 nm for a green color,preferably between 600 nm and 650 nm for a red color. By incorporatingspecific repeating units in the backbone of the polymer the emission canbe even shifted to the near infrared (NIR, >780 nm).

It will be appreciated that the light emissive layer may be formed froma blend or mixture of materials including one or more polymers accordingto the present invention, and optionally further different polymers. Thefurther different polymers may be so-called hole transport polymers(i.e. to improve the efficiency of hole transport to the light-emissivematerial) or electron-transport polymers (i.e. to improve the efficiencyof electron transport to the light-emissive material). Preferably, theblend or mixture would comprise at least 0.1% by weight of a polymeraccording to the present invention, preferably at least 0.5% by weight,more preferably at least 1% by weight.

An organic EL device typically consists of an organic film sandwichedbetween an anode and a cathode such that when a positive bias is appliedto the device, holes are injected into the organic film from the anode,and electrons are injected into the organic film from the cathode. Thecombination of a hole and an electron may give rise to an exciton, whichmay undergo radiative decay to the ground state by liberating a photon.In practice the anode is commonly an mixed oxide of tin and indium forits conductivity and transparency. The mixed oxide (ITO) is deposited ona transparent substrate such as glass or plastic so that the lightemitted by the organic film may be observed. The organic film may be thecomposite of several individual layers each designed for a distinctfunction. Since holes are injected from the anode, the layer next to theanode needs to have the functionality of transporting holes. Similarly,the layer next to the cathode needs to have the functionality oftransporting electrons. In many instances, the hole-(electron)transporting layer also acts as the emitting layer. In some instancesone layer can perform the combined functions of hole and electrontransport and light emission. The individual layers of the organic filmmay be all polymeric in nature or combinations of films of polymers andfilms of small molecules deposited by thermal evaporation. The totalthickness of the organic film be less than 1000 nanometers (nm),especially less than 500 nm. It is preferred that the total thickness beless than 300 nm, while it is more preferred that the thickness of theactive layer is in the range from 40-160 nm.

The ITO-glass, which serves as the substrate and the anode, may be usedfor coating after the usual cleaning with detergent, organic solventsand UV-ozone treatment. It may also be first coated with a thin layer ofa conducting substance to facilitate hole injection. Such substancesinclude copper phthalocyanine, polyaniline (PANI) andpoly(3,4-ethylenedioxy-thiophene) (PEDOT); the last two in their (doped)conductive forms, doped, for example, with FeCl₃ or Na₂S₂O₈. Theycontain poly(styrenesulfonic acid) (PSS) as counter-ion to ensure watersolubility. It is preferred that the thickness of this layer be 200 nmor less; it is more preferred that the thickness be 100 nm or less.

In the cases where a hole-transporting layer is used, the polymericarylamines described in U.S. Pat. No. 5,728,801, may be used. Otherknown hole-conducting polymers, such as polyvinylcarbazole, may also beused. The resistance of this layer to erosion by the solution of thecopolymer film which is to be applied next is obviously critical to thesuccessful fabrication of multi-layer devices. The thickness of thislayer may be 500 nm or less, preferably 300 nm or less, most preferably150 nm or less.

In the case where an electron-transporting layer is used, it may beapplied either by thermal evaporation of low molecular weight materialsor by solution coating of a polymer with a solvent that would not causesignificant damage to the underlying film.

Examples of low molecular weight materials include the metal complexesof 8-hydroxyquinoline (as described by Burrows et al. in Appl. Phys.Lett. 64 (1994) 2718-2720), metallic complexes of10-hydroxybenzoquinoline (as described by Hamada et al. in Chem. Lett.(1993) 906-906), 1,3,4-oxadiazoles (as described by Hamada et al. inOptoelectronics-Devices and Technologies 7 (1992) 83-93),1,3,4-triazoles (as described by Kido et al. in Chem. Lett. (1996)47-48), and dicarboximides of perylene (as described by Yoshida et al.in Appl. Phys. Lett. 69 (1996) 734-736).

Polymeric electron-transporting materials are exemplified by1,3,4-oxadiazole-containing polymers (as described by Li et al. in J.Chem. Soc. (1995) 2211-2212, by Yang and Pei in J. Appl. Phys. 77 (1995)4807-4809), 1,3,4-triazole-containing polymers (as described by Strukeljet al. in Science 267 (1995) 1969-1972), quinoxaline-containing polymers(as described by Yamamoto et al. in Jpn. J. Appl. Phys. 33 (1994)L250-L253, O'Brien et al. in Synth. Met. 76 (1996) 105-108), andcyano-PPV (as described by Weaver et al. in Thin Solid Films 273 (1996)39-47). The thickness of this layer may be 500 nm or less, preferably300 nm or less, most preferably 150 nm or less.

The cathode material may be deposited either by thermal evaporation orby sputtering. The thickness of the cathode may be from 1 nm to 10,000nm, preferably 5 nm to 500 nm.

OLEDs made according to the present invention may include phosphorescentdopants dispersed in the device's emissive layer, capable of achievinginternal quantum efficiencies approaching 100%. As used herein, the term“phosphorescence refers to emission from a triplet excited state of anorganic or metal-organic molecule. High efficiency organic lightemitting devices using phosphorescent dopants have been demonstratedusing several different conducting host materials (M. A. Baldo et al.,Nature, Vol 395, 151 (1998), C. Adachi et al., Appl. Phys. Lett., Vol.77, 904 (2000)).

In a preferred embodiment, the electroluminescent device comprises atleast one hole-transporting polymer film and a light-emitting polymerfilm comprised of the polymer of the invention, arranged between ananode material and a cathode material such that under an appliedvoltage, holes are injected from the anode material into thehole-transporting polymer film and electrons are injected from thecathode material into the light-emitting polymer films when the deviceis forward biased, resulting in light emission from the light-emittinglayer.

In another preferred embodiment, layers of hole-transporting polymersare arranged so that the layer closest to the anode has the loweroxidation potential, with the adjacent layers having progressivelyhigher oxidation potentials. By these methods, electroluminescentdevices having relatively high light output per unit voltage may beprepared.

The term “hole-transporting polymer film” as used herein refers to alayer of a film of a polymer which when disposed between two electrodesto which a field is applied and holes are injected from the anode,permits adequate transport of holes into the emitting polymer.Hole-transporting polymers typically are comprised of triarylaminemoieties. The term “light-emitting polymer film” as used herein refersto a layer of a film of a polymer whose excited states can relax to theground state by emitting photons, preferably corresponding towavelengths in the visible range. The term “anode material” as usedherein refers to a semi-transparent, or transparent, conducting filmwith a work function between 4.5 electron volts (eV) and 5.5 eV.Examples are gold, silver, copper, aluminum, indium, iron, zinc, tin,chromium, titanium, vanadium, cobalt, nickel, lead, manganese, tungstenand the like, metallic alloys such as magnesium/copper,magnesium/silver, magnesium/aluminum, aluminum/indium and the like,semiconductors such as Si, Ge, GaAs and the like, metallic oxides suchas indium-tin-oxide (“ITO”), ZnO and the like, metallic compounds suchas CuI and the like, and furthermore, electroconducting polymers suchpolyacetylene, polyaniline, polythiophene, polypyrrole,polyparaphenylene and the like. Oxides and mixed oxides of indium andtin, and gold are preferred. Most preferred is ITO, especially ITO onglass, or on a plastics material, such as polyester, for examplepolyethylene terephthalate (PET), as substrate.

The term “cathode material” as used herein refers to a conducting filmwith a work function between 2.0 eV and 4.5 eV. Examples are alkalimetals, earth alkaline metals, group 13 elements, silver, and copper aswell as alloys or mixtures thereof such as sodium, lithium, potassium,calcium, lithium fluoride (LiF), sodium-potassium alloy, magnesium,barium, magnesium-silver alloy, magnesium-copper alloy,magnesium-aluminum alloy, magnesium-indium alloy, aluminum,aluminum-aluminum oxide alloy, aluminum-lithium alloy, indium, calcium,and materials exemplified in EP-A 499,011, such as electroconductingpolymers e.g. polypyrrole, polythiophene, polyaniline, polyacetyleneetc. Preferably lithium, barium, calcium, magnesium, indium, silver,aluminum, or blends and alloys of the above are used. In the case ofusing a metal or a metallic alloy as a material for an electrode, theelectrode can be formed also by the vacuum deposition method. In thecase of using a metal or a metallic alloy as a material forming anelectrode, the electrode can be formed, furthermore, by the chemicalplating method (see for example, Handbook of Electrochemistry, pp383-387, Mazuren, 1985). In the case of using an electroconductingpolymer, an electrode can be made by forming it into a film by means ofanodic oxidation polymerization method onto a substrate, which ispreviously provided with an electroconducting coating.

As methods for forming said thin films, there are, for example, thevacuum deposition method, the spin-coating method, the casting method,the Langmuir-Blodgett (“LB”) method, the ink jet printing method and thelike. Among these methods, the vacuum deposition method, thespin-coating method, the ink jet printing method and the casting methodare particularly preferred in view of ease of operation and cost.

In the case of forming the layers by using the spin-coating method, thecasting method and ink jet printing method, the coating can be carriedout using a solution prepared by dissolving the composition in aconcentration of from 0.0001 to 90% by weight in an appropriate organicsolvent such as benzene, toluene, xylene, tetrahydrofurane,methyltetrahydrofurane, N,N-dimethylformamide, acetone, acetonitrile,anisole, dichloromethane, dimethylsulfoxide and mixtures thereof.

Patterning of active matrix OLED (AMOLED) materials for large format,high resolution displays can be done using Laser Induced Thermal Imaging(LITI; Organic Light-Emitting Materials and Devices VII, edited by ZakyaH. Kafafi, Paul A. Lane, Proceedings of SPIE Vol. 5519, 12-23).

The organic EL device of the present invention is seen as a futurereplacement technology for a flat panel display of an on-wall televisionset, a flat light-emitting device, such as a wall paper, a light sourcefor a copying machine or a printer, a light source for a liquid crystaldisplay or counter, a display signboard and a signal light and perhapseven to replace incandescent and fluorescent lamps. The polymers andcompositions of the present invention can be used in the fields of anorganic EL device, a photovoltaic device, an electrophotographicphotoreceptor, a photoelectric converter, a solar cell, an image sensor,and the like.

Accordingly, the present invention relates also to PLEDs, organicintegrated circuits (O-ICs), organic field effect transistors (OFETs),organic thin film transistors (OTFTs), organic solar cells (O-SCs),thermoelectric devices, or organic laser diodes comprising one or moreof the polymers according to the present invention.

The following examples are included for illustrative purposes only anddo not limit the scope of the claims. Unless otherwise stated, all partsand percentages are by weight. Weight-average molecular weight (M_(w))and polydispersity (M_(w)/M_(n)=PD) are determined by Gel PermeationChromatography (GPC) [Apparatus: GPC_(max)+TDA 302 from Viscotek(Houston, Tex., USA) yielding the responses form refractive index (RI),low angle light scattering (LALS), right angle light scattering (RALS)and differential viscosity (DP) measurements. Chromatographicconditions: Column: PL_(get), mixed C (300×7.5 mm, 5 μm particles)covering the molecular weight range from about 1×10³ to about 2.5×10⁶ Dafrom Polymer Laboratories (Church Stretton, UK); Mobile phase:tetrahydrofuran containing 5 g/l of sodium trifluoroacetate; Mobilephase flow: either 0.5 or 0.7 ml/min; Solute concentration: about 1-2mg/ml; Injection volume: 1001; Detection: RI, LALS, RALS, DP. Procedureof molecular weight calibration: Relative calibration is done by use ofa set of 10 polystyrene calibration standards obtained from PolymerLaboratories (Church Stretton, UK) spanning the molecular weight rangefrom 1,930,000 Da-5,050 Da, i.e., PS 1,930,000, PS 1,460,000, PS1,075,000, PS 560,000, PS 330,000, PS 96,000, PS 52,000, PS 30,300, PS10,100, PS 5,050 Da. Absolute calibration is done on the base of theresponses of LALS, RALS and DP. As experienced in a large number ofinvestigations this combination provides optimum calculation ofmolecular weight data. Usually PS 96,000 is used as the molecular weightcalibration standard, but in general every other PS standard lying inthe molecular weight range to be determined can be chosen for thispurpose.

All polymer structures given in the examples below are idealizedrepresentations of the polymer products obtained via the polymerizationprocedures described. If more than two components are copolymerized witheach other sequences in the polymers can be either alternating or randomdepending on the polymerisation conditions.

EXAMPLES Example 1

a) 4-Chloro-2,6-dimethyliodobenzene (9.6 g, 36 mmol) is dissolved inpyrene (60 mL). To this solution, a hot solution of KMnO₄ (28 g, 0.18mol) is poured and the mixture is stirred at 115° C. for 8 hours. Afteradditional heating for 5 hours, a 1M HCl solution is added. Theprecipitate is filtered off and washed with THF. The resultant filtrateis washed with THF and dried over Na₂SO₄. After the evaporation, thedicarboxylic acid derivative is obtained as a solid. Yield 9.1 g (78%).FD-MS (8 kV): m/z=326.7. ¹H NMR (250 MHz, DMSO-d₆) δ ppm 7.24 (s, Ar):¹³C NMR (62.5 MHz, CD₃OD-d₄): δ ppm 126.7, 128.1, 134.5, 150.1, 174.6.

b) The 5-chloro-2-iodo-isophthalic acid (product Example 1a, 3.8 g, 12mmol) is added to SOCl₂ (30 mL, excess) and the mixture is refluxedunder nitrogen for 2 days. The excess SOCl₂ is evaporated under reducedpressure, then the resultant oil containing the5-chloro-2-iodo-isophthaloyl dichloride (4.2 g, 12 mmol) is dissolved indichloromethane (50 mL). To this solution, 1-phenyldodecane (10 g, 47mmol) and AlCl₃ (4.7 g, 35 mmol) are added at 0° C. The mixture isstirred from 0° C. to room temperature overnight. After quenching with1M HCl solution, the residue is extracted by dichloromethane. Themixture is dried over MgSO₄ and purified by column chromatography(silica gel, hexane/ethyl acetate=80:1) to afford thechloro-iododibenzoylbenzene as a colorless oil. Yield 2.3 g (27%). FD-MS(8 kV): m/z=727.7. ¹H NMR (250 MHz, CDCl₃-d) δ ppm 0.88-0.90 (m, 6H,CH₃), 1.26-1.30 (m, 32H, CH₂), 2.69 (t, J=7.3, 4H, CH₂), 7.27-7.41 (m,6H, Ar), 7.75 (t, J=7.9, 4H, Ar); ¹³C NMR (62.5 MHz, CD₂Cl₂-d₂): ¹³C NMR(250 MHz, CD₂Cl₂-d₂): δ ppm 14.3, 23.1, 29.7, 29.8, 29.9, 30.0, 31.4,32.3, 36.5, 128.8, 129.4, 130.9, 132.9, 135.3, 148.2, 151.1, 195.4.

c) Under argon the dibenzoyl derivative (product of example 1b, 0.57 g,0.22 mmol) and copper powder (0.11 g, 1.8 mmol) are added to DMF (10mL). The mixture is stirred at 110° C. for 2 days. After cooling, theresidue is filtered and ethyl acetate and brine are added to thefiltrate. The organic phase is washed with brine three times and driedover MgSO₄. The residue is purified by column chromatography (silicagel, hexane/ethyl acetate=20:1) to afford the biphenylderivative as acolorless oil. Yield 0.52 g (42%). FD-MS (8 kV): m/z=1202.3. ¹H NMR (250MHz, CDCl₃-d) δ ppm 0.81 (m, 12H, CH₃), 1.10-1.20 (m, 64H, CH₂), 2.51(t, J=7.6, 8H, CH₂), 7.02 (d, J=7.9, 8H, Ar), 7.42 (s, 4H, Ar), 7.55 (d,J=7.9, 8H, Ar); ¹³C NMR (62.5 MHz, CD₂Cl₂-d₂): δ ppm 14.3, 21.9, 23.1,29.7, 29.8, 29.9, 30.0, 31.6, 32.3, 36.4, 128.4, 131.2, 131.8, 131.9,134.9, 136.8, 140.9, 149.2, 194.4.

d) Under argon the biphenyldrivative (product of example 1c (0.26 g,0.22 mmol) and bis(tricyclohexyltin)sulfide (0.70 g, 0.91 mmol) aredissolved in toluene (50 mL). To the solution, 1M BCl₃ indichloromethane (0.91 mL, 0.91 mmol) is added. The mixture is stirred atroom temperature for 10 minutes and refluxed at 125° C. for 3 days.After cooling the solvent is evaporated and ethyl acetate and brine areadded to the filtrate. The organic phase is washed with brine threetimes and dried over MgSO₄. The residue is purified by columnchromatography (silica gel, hexane) to afford the new 2,7-dichloropyrenederivative as a powder. Yield 80 mg (33%). FD-MS (8 kV): m/z=1135.9. ¹HNMR (250 MHz, CD₂Cl₂-d₂) δ ppm 0.89 (t, J=6.6, 12H, CH₃), 1.20-1.30 (m,56H, CH₂), 1.50-1.60 (m, 8H, CH₂), 2.62 (t, J=7.3, 8H, CH₂), 7.15 (m,16H, Ar), 7.80 (s, 4H, Ar); ¹³C NMR (175 MHz, CD₂Cl₂-d₂): δ ppm 14.3,23.1, 29.7, 29.8, 29.9, 31.7, 32.4, 36.0, 122.2, 125.1, 128.2, 131.2,132.6, 133.3, 136.3, 138.8, 142.2.

Example 2

a) Synthesis of oligo (2,7-pyrenylene)

A Schlenk tube containing DMF (3.5 mL) and dry toluene (3.5 mL),(1,5-cyclooctadiene)nickel (0) (64 mg, 0.23 mmol), 2,2′-bipyridyl (36mg, 0.23 mmol), and 1,5-cyclooctadiene (28 μL, 0.23 mmol) is heatedunder argon at 80° C. for 30 minutes. The2,7-dichloro-(4,5,9,10-tetraphenyl)-pyrene derivative (product ofexample 1d, 0.11 g, 97 μmol) is dissolved in dry toluene (5 mL) andadded under argon to the solution. The reaction mixture is maintained at80° C. for 3 days in the dark. Bomobenzene (0.1 mL) is added to reactionmixture. The mixture is allowed to react for another day. The reactionmixture is then poured into concentrated hydrochloric acid/methanol 1:1(300 mL). The isolated polymer is dissolved in dichloromethane andreprecipitated in methanol. The residue is purified with a Soxhletextractor to wash off the small molecules for 2 days in acetone. Theresidue is dissolved in THF and precipitated from methanol and dried.Yield 0.056 g (54%). ¹H NMR (250 MHz, C₂D₂Cl₄-d₂) δ ppm 0.86-0.89 (m,CH₃), 1.20-1.40 (m, CH₂), 1.50-1.60 (m, CH₂), 2.59 (t, J=7.3, CH₂),7.00-7.15 (m, Ar), 7.86-7.91 (m, Ar), 8.10 (s, Ar); ¹³C NMR (175 MHz,C₂D₂Cl₄-d₂): δ ppm 13.7, 22.2, 28.6, 28.9, 29.0, 29.2, 30.8, 31.4, 35.1,121.2, 124.3, 127.1, 127.3, 130.2, 131.7, 132.1, 132.4, 135.0, 135.3,138.0, 140.3, 140.7, 140.9.

M_(n)=2600 g/mol; M_(w)=3100 g/mol; PD=1.2 (PPP standard).

b) Synthesis of poly(2,7-pyrenylene)

A sample tube for microwave containing DMF (3 mL) and dry toluene (2mL), (1,5-cyclooctadiene)nickel (0) (58 mg, 0.21 mmol), 2,2′-bipyridyl(33 mg, 0.21 mmol), and 1,5-cyclooctadiene (26 μL, 0.21 mmol) is heatedunder argon at 80° C. for 30 minutes. The 2,7-dichloropyrene derivative(product of example 1d, 0.1 g, 88 μmol) is dissolved in dry toluene (3mL) and added under argon to the solution. The reaction mixture ismaintained and reacted in a microwave at 80° C. (80 W, 60 min).Bromobenzene (0.2 mL) is added to the reaction mixture and the mixtureis allowed to react in the microwave (80 W, 30 min). The reactionmixture is then poured into concentrated hydrochloric acid/methanol 1:1(300 mL). The precipitated polymer is filtered and dissolved indichloromethane and reprecipitated in methanol. The residue is purifiedwith a Soxhlet extractor to wash off the small molecules for 2 days inacetone. The residue is dissolved in THF and precipitated from methanoland dried. Yield 66 mg (66%). ¹H NMR (250 MHz, C₂D₂Cl₄-d₂) δ ppm0.86-0.89 (m, CH₃), 1.20-1.40 (m, CH₂), 1.50-1.70 (m, CH₂), 2.80-2.83(m, CH₂), 6.90-7.25 (m, Ar), 8.00-8.25 (m, Ar); ¹³C NMR (175 MHz,C₂D₂Cl₄-d₂): δ ppm 14.4, 19.9, 21.1, 24.6, 25.0, 25.7, 27.2, 30.3, 32.9,33.3, 34.3, 35.9, 37.2, 37.6, 125.0, 126.5, 127.4, 127.7, 129.1, 129.9,131.1, 131.8, 136.3, 136.3, 136.4, 138.6, 140.6, 149.8.

M_(n)=21800 g/mol; M_(w)=39000 g/mol PD=1.7 (PPP standard)

The absorption maximum in 1,2-dichlorobenzene is observed at 376 nm,while the fluorescence maximum occurs at 429 nm.

Example 3 Poly[2,7-(4,5,9,10-tetraalkoxy)pyrenylene]

A sample tube for microwave containing DMF (2 mL) and dry toluene (2mL), (1,5-cyclooctadiene)nickel (0) (0.13 g, 0.48 mmol), 2,2′-bipyridyl(76 μg, 0.48 mmol), and 1,5-cyclooctadiene (60 μL, 0.48 mmol) is heatedunder argon at 80° C. for 30 minutes. The2,7-dibromo-(4,5,9,10-tetraalkoxy)-pyrene (0.2 g, 0.20 mmol) isdissolved in dry toluene (3 mL) and added under argon to the solution.The reaction mixture is maintained and reacted in a microwave at 80° C.(80 W, 60 min). Bomobenzene (0.2 mL) is added to the reaction mixtureand the mixture is allowed to react in the microwave (80 W, 30 min). Thereaction mixture is then poured into concentrated hydrochloricacid/methanol 1:1 (300 mL). The precipitated polymer is filtered anddissolved in dichloromethane and reprecipitated in methanol. The residueis purified with a Soxhlet extractor to wash off the small molecules for2 days in acetone. The residue is dissolved in THF and precipitated frommethanol and dried. Yield 0.1 g (50%).

¹H NMR (250 MHz, C₂D₂Cl₄) δ ppm 0.75-0.78 (24H, CH₃), 1.05-2.0 (m, CH₃,CH₂), 2.19 (4H, m, CH), 4.59 (m, 8H, OCH₂), 9.05 (m, 4H, Ar).

The GPC analysis yielded molecular weights M_(n)=29700 g/mol M_(w)=58800g/mol and polydispersity PD=2.0 (PPP standard).

The optical properties were measured in THF solution and in thin filmsshowing a maximum of absorption λmax at 371 and 375 nm, respectively.The emission maximum is in the blue range with 441 and 451 nm for thesolution and the film, respectively.

Example 4 a) 2,7-Dibromopyrene-4,5,9,10-tetraone

a) The 4,5,9,10-pyrenetetraone is obtained in one step starting frompyrene according to J. Org. Chem. 2005, 70, 707-708.

3 g of pyrene-4,5,9,10-tetraone are dissolved in 80 ml of conc. H₂SO₄.At room temperature an excess of 2.2 equivalents N-bromosuccinimide(NBS) is added slowly. The reaction mixture is stirred for another hourand finally put in ice water. After precipitation the product isfiltered and washed with water. The crude product is stirred inmethanol, dried and boiled again in ethyl ether and finally inmethylenehloride. 2,7-Dibromopyrene-4,5,9,10-tetraone is obtained in ayield of 78%.

FD-MS (8 KV): m/z 420.1 (100%), calculated 420.0.

¹H-NMR (C₂D₂Cl₄, 250 MHz, 140° C.): d=8.61 (s, 4H).

¹³C-NMR (THF-d8, 175 MHz): d=125.9, 133.4, 134.8, 137.6, 176.3.

b) 2,7-Dibromopyrene-4,5,9,10-tetraalkoxypyrene

A mixture of 2,7-dibromopyrene-4,5,9,10-tetraone (0.50 g, 1.2 mmol),n-Bu₄NBr (0.50 g, 1.5 mmol), Na₂S₂O₄ (2.5 g, 14 mmol), THF (8 mL), andH₂O (4 mL) is stirred at 25° C. for 10 minutes 1-Bromo-2-hexyldecane(1.7 g, 7.9 mmol) and aqueous potassium hydroxide (4 mL, 36 mmol) areadded to the solution and the mixture is stirred at 70° C. for 5 h.Then, THF and brine are added and the organic phase is washed with brine(3 times) and dried over MgSO₄ and concentrated in vacuum. The residueis purified by column chromatography (SiO₂, hexane: CH₂Cl₂=10:1) to givea colorless oil (0.62 g) in 53% yield.

FD-MS (8 KV): m/z 986.3 (100%), calculated 985.1.

¹H-NMR (CD₂Cl₂, 250 MHz): δ=0.84-0.86 (m, 24H), 0.98-1.00 (m, 12H),1.47-2.00 (m, 40H), 4.23-4.36 (m, 8H), 8.50 (s, 4H).

Example 5

a) The synthesis of the 2,7-dibromopyrene is described in J. Org. Chem.1986, 51, 2848. 5.3 g (25 mmol) NalO₄, 25 mL H₂O, and 0.14 g RuCl₃xH₂Oare added to a solution of 1 g (2.8 mmol) 2,7-dibromopyrene in 20 mLCH₂Cl₂ and 20 mL CH₃CN. The dark brown suspension is heated to 50° C.overnight. The reaction mixture is poured into 100 mL of H₂O, andextracted with 100 mL of THF. The organic phase is separated andconcentrated. The crude product 2,7-dibromopyrene-4,5,9,10-tetraone isobtained as red orange substance (yield<15%, m/z 420.0).

Example 6

a) 6,11-dibromo-1,2,3,4-tetraphenyltriphenylene (1.1 g, 1.6 mmol),bis(pinacolato)diboron (0.9 g, 3.5 mmol), AcOK (0.5 g, 4.7 mmol), arecharged in Schlenck flask and dissolved in 17 ml dioxane. The wholemixture is degassed and the catalyst [PdCl₂(dppf)]CH₂Cl₂ (0.065 g, 0.08mmol) is added and the whole reaction mixture is heated up to 90° C. for20 h. The solvent is removed under reduced pressure and the product isfinally purified by chromatography on silica gel withhexane:dichloromethane (1:3), to afford the desired product (0.309 g,25%).

b) A suspension of2,7-di-4,4,5,5-tetramethyl(9,10,11,12-tetraphenyl-triphenylen-2-yl)-[1,3,2]dioxaborolane(0.309 g, 0.39 mmol),2,7-dibromo-4,5,9,10-tetrakis-(3,7-dimethyl-octyloxy)-pyrene (0.388 g,0.39 mmol), aqueous K₂CO₃ (3 ml/2M), Aliquat® 336 (0.04 g, 0.1 mmol),and Pd(PPh₃)₄ (0.023 g, 0.02 mmol) in toluene (4.5 mL) is charged in amicrowave tube equipped with a magnetic stirrer bar, which has beenpurged with argon and sealed. The mixture is vigorously stirred in a CEMDiscover microwave at 50 W and activated cooling; keeping thetemperature at 100° C. for 5 h. Sequentially bromobenzene (0.56 g, 3.6mmol), and benzene boronic acid (0.28 g, 2.3 mmol) in degassed toluene(3 ml) are added to the reaction mixture and stirred at 100° C. for % heach. At room temperature the organic layer is extracted and washed withaqueous sodium cyanide (1%, 2×50 ml). The organic layer is extractedagain with toluene and the solution is concentrated in vacuo until ahigh viscous solution is obtained. The polymer is precipitated by slowaddition to 300 ml methanol. The polymer is filtered off andsequentially washed with methanol, water, acetone, and methanol. Thepolymer is dissolved again in toluene and vigorously stirred in aqueoussodium cyanide (1%, 100 ml) at 90° C. for 2 h. The organic phase isextracted, concentrated, and finally poured into an excess of methanol.The polymer is filtered off, and the oligomeric fractions are removed byextraction (1 day/Soxhlet apparatus/ethyl acetate). Yield of polymer:0.28 g (52%).

GPC analysis: M_(w)=12.4×103 g mol⁻¹, PDI=1.4 (PPP standard).

1-9. (canceled)
 10. A compound of the formula

wherein R¹, R², R³, R⁴, R⁵ and R⁶ are independently of each other F,SiR¹⁰⁰R¹⁰¹R¹⁰², or an organic substituent, or R¹ and R², R³ and R⁴,and/or any of the substituents R¹, R², R³, R⁴, R⁵ and/or R⁶, which areadjacent to each other, together form an aromatic, or heteroaromaticring, or ring system, which can optionally be substituted, m is 0, or aninteger of 1, or 2, n₁ and n₂ are 0, or an integer 1, or 2, R¹⁰⁰, R¹⁰⁰and R¹⁰² are independently of each other C₁-C₁₈alkyl, substituted orunsubstituted C₆-C₁₈aryl, and Ar¹ and Ar² are each independently of eachother a substituted or unsubstituted arylene, or heteroarylene group,X¹¹ is independently in each occurrence a halogen atom, —ZnX¹²,—SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or differentand are H or C₁-C₆alkyl, wherein two radicals optionally form a commonring and these radicals are optionally branched or unbranched and X¹² isa halogen atom; or —OS(O)₂CF₃, —OS(O)₂-aryl, OS(O)₂CH₃, —B(OH)₂,—B(OY¹¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y¹² is independently in each occurrence—CY¹³Y¹⁴—CY¹⁵Y¹⁶— or —CY¹⁷Y¹⁸—CY¹⁹Y²⁰—CY²¹Y²²—, wherein Y¹³, Y¹⁴, Y¹⁵,Y¹⁶, Y¹⁷, Y¹⁸, Y¹⁹, Y²⁰, Y²¹ and Y²² are independently of each otherhydrogen, or a C₁-C₁₀alkyl group,


11. A compound of the formula wherein X¹¹, Ar¹, Ar², n₁, n₂, R⁵, R⁶ andm are as defined in claim
 10. 12. A process for preparing a compound ofthe formula

comprising reacting a compound of formula

with a brominating agent, which is N-bromosuccinimide (NBS) or1,3-bromo-5,5-dimethyldantoin, wherein X¹¹ is Br, n₁ and n₂ are 0, Ar¹,Ar², R⁵, R⁶ and m are as defined in claim
 10. 13. The compound accordingto claim 10, wherein R¹, R², R³ and R⁴ are independently of each otherC₆-C₁₂aryl, or C₂-C₁₁heteroaryl, which are optionally substituted by oneor more groups G, wherein G is as defined in claim 2, or R¹, R², R³ andR⁴ are independently of each other C₁-C₁₈alkyl, C₁-C₁₈alkyl which isinterrupted by —O—, C₁-C₁₈alkoxy; or C₁-C₁₈alkoxy which is interruptedby —O—.
 14. The compound according to claim 13, wherein R¹, R², R³ andR⁴ are independently of each other

wherein n3 is 0, or an integer 1, 2, 3, 4, or 5, R¹¹ can be same, ordifferent in each occurrence and is C₁-C₂₅alkyl, or C₁-C₂₅alkoxy, or R¹,R², R³ and R⁴ are independently of each other C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is interrupted by —O—, C₁-C₁₈alkoxy; or C₁-C₁₈alkoxy which isinterrupted by —O—.
 15. The compound according to claim 10, wherein X¹¹is independently I, Cl, Br or —ZnX¹², wherein X¹² is I, Br, —OS(O)₂CF₃,or


16. The compound according to claim 10, wherein Y¹³, Y¹⁴, Y¹⁵, Y¹⁶, Y¹⁷,Y¹⁸, Y¹⁹, Y²⁰, Y²¹ and Y²² are independently —C(CH₃)₂C(CH₃)₂—, or—C(CH₃)₂CH₂C(CH₃)₂.